WO2015099529A1 - Process and apparatus for recycling asbestos-containing steel scrap - Google Patents
Process and apparatus for recycling asbestos-containing steel scrap Download PDFInfo
- Publication number
- WO2015099529A1 WO2015099529A1 PCT/NL2014/050900 NL2014050900W WO2015099529A1 WO 2015099529 A1 WO2015099529 A1 WO 2015099529A1 NL 2014050900 W NL2014050900 W NL 2014050900W WO 2015099529 A1 WO2015099529 A1 WO 2015099529A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- asbestos
- steel
- scrap
- steel scrap
- air
- Prior art date
Links
- 239000010425 asbestos Substances 0.000 title claims abstract description 125
- 229910052895 riebeckite Inorganic materials 0.000 title claims abstract description 125
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 118
- 239000010959 steel Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008569 process Effects 0.000 title claims abstract description 27
- 238000004064 recycling Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000161 steel melt Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005266 casting Methods 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 9
- 238000010891 electric arc Methods 0.000 claims description 8
- 239000000155 melt Substances 0.000 claims description 8
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000009423 ventilation Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 238000010079 rubber tapping Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000013022 venting Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 30
- 230000006378 damage Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 230000032258 transport Effects 0.000 description 13
- 239000002699 waste material Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 239000012634 fragment Substances 0.000 description 3
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- 239000002920 hazardous waste Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 238000010309 melting process Methods 0.000 description 3
- 150000003071 polychlorinated biphenyls Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- 239000011734 sodium Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 2
- -1 aluminum (AT) Chemical class 0.000 description 2
- 229910052612 amphibole Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011819 refractory material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 208000033116 Asbestos intoxication Diseases 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000019693 Lung disease Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 229910004553 Na2Fe2 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052891 actinolite Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052885 anthophyllite Inorganic materials 0.000 description 1
- 206010003441 asbestosis Diseases 0.000 description 1
- 238000009435 building construction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052620 chrysotile Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- NPUJHQNGUMWIMV-UHFFFAOYSA-L dicalcium pentamagnesium [dioxido-[oxo(trioxidosilyloxy)silyl]oxysilyl]oxy-[[dioxido-[oxo(trioxidosilyloxy)silyl]oxysilyl]oxy-oxosilyl]oxy-dioxidosilane dihydroxide Chemical compound [OH-].[OH-].[Mg++].[Mg++].[Mg++].[Mg++].[Mg++].[Ca++].[Ca++].[O-][Si]([O-])([O-])O[Si](=O)O[Si]([O-])([O-])O[Si](=O)O[Si]([O-])([O-])O[Si]([O-])([O-])O[Si](=O)O[Si]([O-])([O-])[O-] NPUJHQNGUMWIMV-UHFFFAOYSA-L 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000009845 electric arc furnace steelmaking Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 208000006178 malignant mesothelioma Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000013520 petroleum-based product Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100000701 toxic element Toxicity 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- ULEFFCDROVNTRO-UHFFFAOYSA-N trimagnesium;disodium;dihydroxy(oxo)silane;iron(3+) Chemical compound [Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Fe+3].[Fe+3].O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O.O[Si](O)=O ULEFFCDROVNTRO-UHFFFAOYSA-N 0.000 description 1
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/0066—Disposal of asbestos
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
- C21C5/56—Manufacture of steel by other methods
- C21C5/562—Manufacture of steel by other methods starting from scrap
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/10—Handling in a vacuum
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/10—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating electric
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/061—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating
- F23G7/065—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases with supplementary heating using gaseous or liquid fuel
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
- F27B3/085—Arc furnaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/36—Plugs, connectors, or parts thereof
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2100/00—Exhaust gas
- C21C2100/02—Treatment of the exhaust gas
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C2200/00—Recycling of waste material
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/20—Combustion to temperatures melting waste
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2900/00—Special features of, or arrangements for incinerators
- F23G2900/70—Incinerating particular products or waste
- F23G2900/7005—Incinerating used asbestos
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2217/00—Intercepting solids
- F23J2217/10—Intercepting solids by filters
- F23J2217/103—Intercepting solids by filters ultrafine [HEPA]
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J2900/00—Special arrangements for conducting or purifying combustion fumes; Treatment of fumes or ashes
- F23J2900/15002—Cleaning fumes by letting them to pass a molten metal bath
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
- F27B3/10—Details, accessories, or equipment peculiar to hearth-type furnaces
- F27B3/20—Arrangements of heating devices
Definitions
- the invention is in the field of recycling. More particularly the invention is in the field of processing steel scrap that has been contaminated with asbestos.
- Asbestos is known as a material used in construction to provide mechanical strength and fire resistance. Because of its low thermal conduction capabilities and therefore its heat and fire resistance, it has been incorporated in a wide variety of constructions in various forms, amongst others in the sectors of building construction and mechanical engineering.
- asbestos disposal should be carried out with utmost precautions.
- the current disposal of asbestos containing materials comprises disposing thereof in special regulated dumping sites. This disposal methodology requires large disposal volumes, especially if the asbestos is present in other objects, such as pipes covered with asbestos or pieces of metal to which asbestos is attached, e.g. by an adhesive.
- EP-A-1 277 527 discloses a method to dispose of asbestos, which involves placing the initial product as pieces in a tunnel oven at a
- JP-A-2004/204261 describes a recycling method for scrap of building materials generated on a dismantling field in which iron resources can be recovered.
- contaminated scrap is classified in fractions including resin content scrap and asbestos content scrap.
- the asbestos containing scrap is charged in small quantities in a processing furnace, which is filled with molten iron obtained from an essentially non-contaminated fraction.
- the classification of the different fractions requires handling, which may result in asbestos being emitted into the environment.
- only small quantities of 2 tons or less of asbestos contaminated steel can be processed by mixing it in an existing steel melt.
- US-A-2007/0251607 describes a process for handling fragments that are contaminated with asbestos, which requires a step of coating the fragments to immobilize the asbestos particles. Coating the fragments is an extra step, requiring extra handling, which increases the risk of asbestos particles being emitted into the atmosphere.
- WO-A-98/03830 describes an approach for melting a railway car contaminated with asbestos, which involves the entire railway car being put into a melting unit. No measures are described to avoid spreading of asbestos into the environment.
- WO-A-97/33840 describes processing asbestos containing waste in a vitrification method.
- the materials are bagged in plastic bags, which are subsequently milled. Apart from the step of bagging, no measures appear to be described to avoid spreading of asbestos into the environment, in particular not in the milling step.
- DE-A-44 07 339 describes processing asbestos containing waste from buildings and building materials.
- the waste material is sealed inside a container, in particular a steel container. No other measures are taken to avoid spreading of asbestos particles into the environment.
- GB-A-0 817 414 relates to the field of casting of titanium and other reactive metals. Vacuum is used for the removal of air (oxygen) from the room that surrounds the furnace.
- AT-A-411818 describes the disposal of asbestos waste packed in pressure vessels by melting the pressure vessels in a furnace. The inside of vessels is sealed from the outside and as such no asbestos can escape before the waste is loaded into the furnace. Hence, the method described in AT-A- 411818 is only safely applicable to asbestos waste sealed in pressure vessels.
- US-A-5 662 050 describes a rotary kiln to treat toxic or hazardous waste and to produce "glass-like” or “ceramic -like” end products. No treatment of steel waste with asbestos is described and consequently no homogeneous steel scrap product that is free of asbestos is obtained.
- GB-A-2445420 relates to the treatment of hazardous waste components such as asbestos. However, no measures are taken to avoid spreading of asbestos particles into the environment.
- JP-A-2008/249220 describes melting and detoxifying asbestos- containing waste metal but does not describe the cooling of the molten metal or the recovery of said metal.
- US-A-5370066 describes an apparatus in which hazardous waste material is molten.
- the molten waste is solidified into inorganic ceramic- like aggregate material.
- JP-A-2007/307548 is directed to a method for melting asbestos waste.
- the molten waste does not appear to be cooled to produce a specific product.
- Such a method should not emit toxic compounds into the environment that are normally associated with asbestos and the processing thereof, such as poly chlorinated biphenyls (PCBs), petroleum based products, paints, coatings, and the like.
- PCBs poly chlorinated biphenyls
- the asbestos-containing steel scrap is melted in a furnace, which results in destruction of the asbestos fibers. It has been found possible to carry out such a process in an economically feasible manner.
- asbestos-containing steel is heated to high temperature so that the steel melts. This is preferably done by submerging the asbestos-containing steel into an existing melt.
- the step wherein the asbestos containing scrap is fed to the melt is carried out sealed from the environment in a substantially gas-tight manner.
- the asbestos will be converted into harmless material without asbestos fibers being emitted to the environment, which allows for safe handling and processing of the resulting products.
- the invention is directed to a process for recycling asbestos- containing steel scrap, which scrap comprises a combination of steel and asbestos, which process comprises the steps of:
- steps a) and b) are carried out in a room that is sealed off from the environment in a substantially gas-tight manner, so as to substantially prevent emission of fibers.
- the invention provides a method for recycling asbestos- containing steel scrap into purified metal blocks, without emitting asbestos fibers to the environment and at a low cost.
- the steel scrap may also be contaminated with toxic components like PCBs or petroleum based coatings. Emission of toxic elements resulting from the toxic components is also preferably avoided.
- the scale of the operation can be industrial scale, typically with a capacity of more than 200 kiloton per year, preferably more than 300 kiloton, typically up to 750 kiloton per year.
- substantially prevented is meant that the steel scrap product contains no asbestos fibers in any amount that would be considered harmful or dangerous. In particular any fibers still present in said product should be immobilized therein, so that no harmful amounts of fibers can become airborne, thus substantially preventing emission of asbestos fibers therefrom. When emission of fibers is said to be
- concentration in the surrounding atmosphere remains below safety standards, in particular below 1000 fibers per m 3 , more preferably below 500 fibers per m 3 . Such conditions are considered to result in a safe working environment by most international standards. More preferably the
- concentration of fibers is as low as about 20-40 fibers per m 3 , which is the generally accepted to be the background level of asbestos fibers.
- the steps of feeding the contaminated scrap to a melt and allowing the contaminated steel to melt are sealed off from the environment. This is done by carrying out these steps in a room that is sealed off from the environment in a substantially gas-tight manner.
- the substantially gas-tight manner relates to measures to avoid outflow of air contaminated with asbestos particles. This may for instance be effected by maintaining the pressure inside of said room below 1 atm. Typically the pressure is about 0.05-0.1 bar below atmospheric pressure. By maintaining the pressure of said room below atmospheric pressure, an air flow from outside to inside the room will limit air being able to flow from inside to outside the room.
- This principle can be tested in a laboratory.
- a small piece of scrap typically about 500 g, which is contaminated with an asbestos layer of known composition and weight, is fed into a small furnace with a molten steel bath, which furnace is then sealed of in a gastight manner.
- the off-gas of the furnace is carefully measured and controlled.
- a HEPA filter is able to catch any asbestos fiber in the off-gas that was not melted in the liquid steel bath.
- the HEPA filter can be checked on asbestos fibers with an electron microscope (TEM or SEM), and the off- gas chemical composition can be checked.
- HEPA particulate air
- the process furthermore comprises an off- gas burning system.
- the off- gas burning system is a known technique that is used to capture particles from a gas stream. In a normal off-gas burner the off-gas is heated to a high temperature, e.g. from 700-900 °C, typically approximately 800 °C.
- the temperature of the off-gas in the off-gas burning step is chosen much higher, for instance above 1200 °C, e.g. 1250-1350 °C, which will destroy any resulting asbestos particles.
- the gases After heating up the gases to a high temperature, for instance 1200 °C, the gases should be cooled. Cooling is done rapidly to avoid formation of dioxins and furans. To this end cooling is done preferably to a temperature lower then 500 °C, more preferably below 200 °C. Within the temperature range 200-600 °C dioxins and furans are formed, the most critical range for the formation of these compounds being 200-400 °C. Most preferably the cooling rate in the range 200-400 °C is at least 100 °C/s.
- Preferably cooling is done in two steps.
- the first cooling step typically down to 400 °C can be done relatively slow.
- the second step from 400 °C to 200 °C, is preferably done rapidly, typically within 2 seconds, to prevent forming of dioxins and furans again (de novo synthesis).
- the casting area is located in a different room than the furnace area where melting takes place. In this way the casting can be done at a different pressure than the melting. Preferably the casting is done at atmospheric pressure, while the melting is done at subatmospheric pressure, as explained above.
- the casting area can be located at a lower level so that the molten steel can flow to it by its own weight, which is the easiest way to transport molten steel.
- contaminated objects into small pieces locally, immediately into gas-tight containers.
- containers may hold approximately 4-8 tons of contaminated steel.
- the gas-tight, in particular airtight, containers are transported to the facility that holds the melting steps of the present invention, and enters said facility while maintaining an underpressure to avoid any asbestos particles flowing out.
- the containers can be opened and their contents can be transferred into the molten liquid steel bath.
- the containers are emptied in a bunker, for instance via a conveyer belt.
- Another conveyor belt can be used to transport the
- the contaminated scrap on the conveyer belt can be preheated. Preheating can be done on the conveyer belt, which transports the scrap into the furnace. Alternatively the scrap can be preheated with a so called “shaft principle", where the scrap is preheated in a separate compartment on top of the furnace. Also other pre- heating techniques can be used.
- the optionally preheated scrap is subsequently fed smoothly to the liquid steel bath, without emitting asbestos fibers to the environment.
- the technique concerning a preheated conveyer belt is proven and readily commercially available.
- the container is closed, brought outside the melting room, where it may be cleaned, so that it is ready to hold the next batch of contaminated steel.
- Scrap can be classified in various ways. The highest level of specification is to distinguish the source of the scrap directly from steel processing (new scrap), and scrap from products after their use (old scrap).
- New scrap is generated during the initial manufacturing processes and in average does not need any pre-treatment besides cutting.
- Old scrap is collected after a use cycle, either separately or mixed, and is often contaminated to a certain degree, depending highly on its origin and the collection systems used.
- This invention is focused on this category of scrap, wherein the scrap is contaminated with asbestos.
- Asbestos-contaminated steel scrap is commonly used in all categories but mainly in the first two.
- the present invention is for instance suitable for processing asbestos-contaminated scrap from railroad carriages, which traditionally contain considerable amount of asbestos adhered to the steel body, in particular in the form of sound deadening panels.
- the steel scrap is usually separated whenever possible along the dismantling process and is sold for direct re-use or to traders or treatment plants.
- Scrap that is contaminated with asbestos normally ends up in official dumping places where it is stored, isolated from the environment, typically in double plastic packaging material. Because this is expensive the contaminated scrap is often illegally shipped through export, which poses serious environmental concerns.
- a notorious example is the beaching of asbestos contaminated ships on shores of developing countries.
- asbestos-containing steel is heated so that the steel melts.
- the asbestos will degrade, in particular the asbestos crystals will be converted into amorphous materials, such as silicates and optionally other salts.
- the heating and melting of the asbestos-containing scrap is preferably done using an electric arc furnace heating process.
- First scrap steel is loaded into air-tight containers at the storage location without exposing the environment to its content.
- the containers are designed in such way that they will open above the conveyer belt, which conveyer belt transports and releases the scrap into the bunker. From the bunker, another conveyer belt is fed with contaminated scrap, which conveyer belt transports the scrap from the bunker smoothly into the furnace.
- the logistic process is described hereinbelow.
- the furnace may for instance be a basic oxygen furnace, an open-hearth furnace or an electric arc furnace. It is important that the furnace allows for constant flat bath operation.
- an electric arc furnace is used.
- the invention allows for different processing, depending on the degree of contamination of the steel scrap. All types of asbestos- contaminated steel scrap must be considered dangerous to the environment and human health as a result of air emissions from one or more source categories. The contaminated steel scrap is therefore treated in such way that the risk exposure to the environment or humans is excluded.
- the invention may be used for treatment of steel that is contaminated with non-friable asbestos, as well as with friable asbestos.
- the furnace is charged with steel scrap, which is molten to produce a furnace filled with a melt.
- the melt typically has a temperature of about 1500-1700 °C. Higher temperatures are not preferred because this may cause damage to the refractory material.
- the steel melt may be poured into a ladle. This process is called tapping. After the first heat is tapped a small amount of steel liquid is left behind into the furnace. The ladle transports the liquid steel to a casting area with separate molds or to a continuous casting area. In these areas the liquid steel is poured into molds or transferred to a casting system to obtain the desired shape of the metal blocks. This process is called casting.
- stripping After solidification in the molds the formed steel scrap blocks are removed therefrom, this process is referred to as stripping. After stripping a purified metal block of steel scrap is obtained, and it is possible to have a detailed specifications of its content. These blocks may then be stored or directly transported e.g. to steel mills to be further processed. Typically these blocks are purchased by steel mills or scrap yards. Because these blocks may have a known composition, and this composition can be made available together with a batch of blocks of the same composition, these blocks can be blended with steel melts to alter the composition thereof in a predetermined manner.
- the small amount of liquid steel left behind in the furnace is to make sure that a second load of contaminated steel scrap when deposited in the furnace will be completely submerged into the liquid steel bath. It is essential because in this way the scrap and the asbestos is directly confronted with a temperature of liquid metal of at least 1500 °C and it will take fractions of seconds to degrade the asbestos and make it harmless.
- the asbestos-containing steel scrap starting material of the present invention is typically steel, e.g. in the form of plates or pipes, which is combined with asbestos, typically by means of an adhesive, such as a polyurethane or acrylate based adhesive.
- an adhesive such as a polyurethane or acrylate based adhesive.
- Asbestos is made up of relative long and thin crystalline silicate mineral fibers. Apart from silicate, the crystals further contain hydroxy! (OH-), and further magnesium (Mg) and/or iron (Fe) and possibly sodium (Na) and/or calcium (Ca).
- Mg magnesium
- Fe iron
- Na sodium
- Ca calcium
- Six minerals are defined as "asbestos", which can be divided into the serpentine class or those belonging to the amphibole class.
- the serpentine class comprises: chrysotile, Mg3(Si205)(OH)4.
- the amphibole class comprises: amosite, Fe 7 Si8022(OH)2; crocidolite, Na2Fe 2+ 3Fe 3+ 2Si8022(OH)2; tremolite asbestos, Ca2Mg5Sis022(OH)2; actinolite asbestos, Ca2(Mg, Fe)5(Sis022)(OH)2; and anthophyllite asbestos (Mg,
- Asbestos generally degrades between 400 °C and 800 °C, although some asbestos types require temperatures up to 1040 °C.
- the crystals lose their crystalline integrity and the chemical components are converted into their corresponding salts (mostly oxides), such as S1O2 and MgO, as well as H2O, which will evaporate.
- the amorphous salts may either stay in the melt and end up in the ingots as inclusions, but the majority will be transferred to the slag phase. In either case the materials will be present as harmless amorphous particles.
- a slag is formed by diffusion. This slag floats on the surface of the molten steel.
- Slag usually consists of metal oxides, and acts in particular as a destination for oxidized impurities. These impurities may be metallic or non-metallic impurities.
- slag comprises as the majority compounds calcium oxide (CaO) and magnesium oxide (MgO).
- CaO calcium oxide
- MgO magnesium oxide
- Another major component of electric arc furnace slag is iron oxide from steel combusting with oxygen that is injected to provide extra chemical heat for melting the steel and to stimulate the oxidation of impurities (refining).
- the thus obtained slag is removed and further processed to recover metals contained therein which gives further economic and environmental benefits.
- the slag is optionally further processed into different types of fractions.
- the slag may be used in construction, e.g. in the construction of roads.
- the chemical elements originating from the asbestos were found to have a positive effect on the quality of the slag for the purpose of road building.
- An apparatus in accordance with the present invention which is very suitable for the method described herein, typically comprises the following components.
- EAF electric arc furnace
- the capacity of the furnace is more than 25 ton, preferably between 40 and 100 tonnes
- an off-gas cleaning system suitable for EAF, comprising a post- combustion chamber that is able to heat up off-gas, typically up to 1200 °C, and a cooling apparatus that is able to cool the off-gas very rapidly to a temperature lower than 200 °C
- an air ventilation system suitable for EAFs, capable of maintaining the air pressure lower than the outside building air pressure; typically the underpressure is between 0.05 and 0.1 below atmospheric pressure;
- weights of the ingots are 0.5 ton and 1 ton
- the housing for the entire installation is constructed in such way that, in combination with the air ventilation system, a shght under pressure in the building can be maintained at all times. By the construction transport of asbestos fibers from the housing to the environment is prevented.
- the invention provides for a safe and economical viable method of degrading asbestos.
- the installations are typically placed in a special designed building. Within this building an under pressure can be maintained at all times, in combination with the air ventilation system.
- the slight under pressure provides a second safety layer to protect the environment from asbestos fibers. In the unlikely situation that asbestos fibers would escape from the liquid steel scrap melt without degrading, the under pressure prevents fibers to be transported to the outside environment. Secondly, any fibers that are taken in by the ventilation system, will be caught by the HEPA filter unit.
- the transport of the asbestos contaminated scrap starts at the source.
- the object that contains contaminated asbestos steel should be inspected, typically through specialized firms, which will determine the level of contamination and apply a suitable code for transport.
- the object may contain different types of steel.
- Steel grades are divided in three classes according to the European Commission's End of Waste Regulation: - Unalloyed steel grades in which the mass fraction of an alloying element remains below a certain critical value.
- stainless steel which is a generic term for a group of corrosion- resistant steel containing a minimum of 10.5% chromium.
- the types of stainless steel can be divided in ferritic, martensitic, austenitic and duplex; each category containing its own critical specifications. Varying additions of nickel, molybdenum, titanium, niobium and other elements may be present.
- alloyed steel grades refer to steel grades that fall outside the above mentioned definitions. Alloy quality steels comprise steel grades required to meet certain requirements related to the aspect of the
- the steel scrap should be collected in such manner that the analysis of the different types of steel scrap are maintained as homogeneous as possible.
- the steel asbestos-contaminated scrap is collected in containers, typically small containers (for instance between 4 and 8 tonnes).
- the small containers will be put on transportation where it will be stored in a separated closed building, while maintaining underpressure.
- the containers will be emptied in a bunker within the building where they are collected, albeit separated from the melting room, at a lower than atmospheric pressure in order to prevent fibres to be released to the environment.
- the invention supports the ultimate sustain ability of steel scrap by eliminating the asbestos from the supply chain and preventing the steel scrap being dumped.
- the invention can also be used to clear existing dumps by processing the contaminated scrap contained therein.
- the invention not only provides new raw material possibilities in the shape of steel but elements like nickel, molybdenum, wolfram and other elements can be recycled as well.
- the products of the present invention can be used to provide different steel mills with new raw material.
- the new cleaned steel scrap has upgraded commercial value and may be provided with a certificate of analysis indicating its chemical composition. The value differs from current scrap categories because it is homogeneous and provided with analysis.
- the products of the invention can be sold as high-quality scrap, i.e. material to be used in steel mills for altering the composition of steel melts.
- the high quality is derived from the fact that the chemical composition can be known, since the product is homogeneous, as opposed to normal scrap, which is inhomogeneous and therefore has an unknown exact composition.
- the invention provides a short chain of transportation which is very easy to control.
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Treating Waste Gases (AREA)
- Vertical, Hearth, Or Arc Furnaces (AREA)
- Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
Abstract
Description
Claims
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP14828349.2A EP3089829B1 (en) | 2013-12-23 | 2014-12-23 | Process for recycling asbestos-containing steel scrap |
DK14828349.2T DK3089829T3 (en) | 2013-12-23 | 2014-12-23 | PROCEDURE FOR RECYCLING STEEL WASTE CONTAINING ASBEST |
RSP20191011 RS59261B1 (en) | 2013-12-23 | 2014-12-23 | Process for recycling asbestos-containing steel scrap |
PL14828349T PL3089829T3 (en) | 2013-12-23 | 2014-12-23 | Process for recycling asbestos-containing steel scrap |
ES14828349T ES2742082T3 (en) | 2013-12-23 | 2014-12-23 | Asbestos-containing steel scrap recycling process |
LTEP14828349.2T LT3089829T (en) | 2013-12-23 | 2014-12-23 | Process for recycling asbestos-containing steel scrap |
AU2014370511A AU2014370511B2 (en) | 2013-12-23 | 2014-12-23 | Asbestos processing |
SI201431304T SI3089829T1 (en) | 2013-12-23 | 2014-12-23 | Process for recycling asbestos-containing steel scrap |
JP2016540968A JP6599869B2 (en) | 2013-12-23 | 2014-12-23 | Process and apparatus for reprocessing asbestos-containing steel scrap |
CA2934498A CA2934498C (en) | 2013-12-23 | 2014-12-23 | Asbestos processing |
BR112016014806A BR112016014806A2 (en) | 2013-12-23 | 2014-12-23 | PROCESS AND APPARATUS FOR RECYCLING STEEL SCRAP CONTAINING ASBESTOS |
US15/104,289 US10400295B2 (en) | 2013-12-23 | 2014-12-23 | Asbestos processing |
HRP20191426 HRP20191426T1 (en) | 2013-12-23 | 2019-08-07 | Process for recycling asbestos-containing steel scrap |
CY20191100857T CY1122068T1 (en) | 2013-12-23 | 2019-08-09 | PROCESS FOR THE RECYCLING OF ASBESTOS WASTE STEEL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL2013050950 | 2013-12-23 | ||
NLPCT/NL2013/050950 | 2013-12-23 |
Publications (1)
Publication Number | Publication Date |
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WO2015099529A1 true WO2015099529A1 (en) | 2015-07-02 |
Family
ID=49956327
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2014/050900 WO2015099529A1 (en) | 2013-12-23 | 2014-12-23 | Process and apparatus for recycling asbestos-containing steel scrap |
Country Status (16)
Country | Link |
---|---|
US (1) | US10400295B2 (en) |
EP (1) | EP3089829B1 (en) |
JP (1) | JP6599869B2 (en) |
AU (1) | AU2014370511B2 (en) |
BR (1) | BR112016014806A2 (en) |
CA (1) | CA2934498C (en) |
CY (1) | CY1122068T1 (en) |
DK (1) | DK3089829T3 (en) |
ES (1) | ES2742082T3 (en) |
HR (1) | HRP20191426T1 (en) |
HU (1) | HUE046064T2 (en) |
PL (1) | PL3089829T3 (en) |
PT (1) | PT3089829T (en) |
RS (1) | RS59261B1 (en) |
SI (1) | SI3089829T1 (en) |
WO (1) | WO2015099529A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021081682A1 (en) | 2019-10-28 | 2021-05-06 | Rudanac Biotec Spa | Method for biodisintegrating scrap metal using a bacterial consortium adapted to high concentrations of iron(ii) sulfate and iron(iii) sulfate |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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FR3025732B1 (en) * | 2014-09-15 | 2019-05-31 | Pyro Green Innovations | PROCESS AND INSTALLATION FOR CONTINUOUS VITRIFICATION OF FIBROUS MATERIALS |
EP3957939B1 (en) | 2020-08-20 | 2023-09-20 | ABP Induction Systems GmbH | Assembly for recycling contaminated metal scrap |
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2014
- 2014-12-23 SI SI201431304T patent/SI3089829T1/en unknown
- 2014-12-23 DK DK14828349.2T patent/DK3089829T3/en active
- 2014-12-23 BR BR112016014806A patent/BR112016014806A2/en not_active Application Discontinuation
- 2014-12-23 HU HUE14828349A patent/HUE046064T2/en unknown
- 2014-12-23 WO PCT/NL2014/050900 patent/WO2015099529A1/en active Application Filing
- 2014-12-23 PT PT14828349T patent/PT3089829T/en unknown
- 2014-12-23 EP EP14828349.2A patent/EP3089829B1/en active Active
- 2014-12-23 AU AU2014370511A patent/AU2014370511B2/en active Active
- 2014-12-23 JP JP2016540968A patent/JP6599869B2/en active Active
- 2014-12-23 PL PL14828349T patent/PL3089829T3/en unknown
- 2014-12-23 RS RSP20191011 patent/RS59261B1/en unknown
- 2014-12-23 US US15/104,289 patent/US10400295B2/en active Active
- 2014-12-23 CA CA2934498A patent/CA2934498C/en active Active
- 2014-12-23 ES ES14828349T patent/ES2742082T3/en active Active
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- 2019-08-09 CY CY20191100857T patent/CY1122068T1/en unknown
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JP2017502828A (en) | 2017-01-26 |
HUE046064T2 (en) | 2020-02-28 |
EP3089829B1 (en) | 2019-05-22 |
ES2742082T3 (en) | 2020-02-13 |
BR112016014806A2 (en) | 2017-08-08 |
AU2014370511B2 (en) | 2018-11-15 |
JP6599869B2 (en) | 2019-10-30 |
HRP20191426T1 (en) | 2019-11-15 |
US20160376673A1 (en) | 2016-12-29 |
CY1122068T1 (en) | 2020-11-25 |
EP3089829A1 (en) | 2016-11-09 |
PL3089829T3 (en) | 2019-11-29 |
PT3089829T (en) | 2019-08-29 |
DK3089829T3 (en) | 2019-08-19 |
SI3089829T1 (en) | 2019-10-30 |
CA2934498C (en) | 2022-03-29 |
US10400295B2 (en) | 2019-09-03 |
AU2014370511A1 (en) | 2016-07-28 |
CA2934498A1 (en) | 2015-07-02 |
RS59261B1 (en) | 2019-10-31 |
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